Efficient and streamlined synthetic methods that facilitate the rapid build-up of structurally diverse π-conjugated systems are paramount importance in quest for organic optoelectronic materials. Among these methods, transition-metal-catalyzed oxidative Ar–H/Ar–H coupling reactions between two (hetero)arenes have emerged as a concise effective approach generating wide array bi(hetero)aryl fused heteroaryl structures. This innovative bypasses challenges associated with substrate...

Fully loaded: A coordinating activation strategy has been developed to furnish α-quaternary α-amino acids through the iron(III)-catalyzed oxidative functionalization of α-C(sp3)H bonds α-tertiary acid esters. The reaction exhibits a broad substrate scope for both and nucleophiles (Nu) as well good functional-group tolerance (see scheme, DTBP=di-tert-butyl peroxide, DCE=1,2-dichloroethane). α,α-Disubstituted are prominent structural units many natural products, pharmaceuticals, bioactive...

Abstract The first example of cobalt‐catalyzed oxidative C−H/C−H cross‐coupling between two heteroarenes is reported, which exhibits a broad substrate scope and high tolerance level for sensitive functional groups. When the amount Co(OAc) 2 ⋅4 H O reduced from 6.0 to 0.5 mol %, an excellent yield still obtained at elevated temperature with prolonged reaction time. method can be extended arene heteroarene. It worth noting that Ag CO 3 oxidant renewable. Preliminary mechanistic studies by...

Radical addition reactions of olefins have emerged as an attractive tool for the rapid assembly complex structures, and plentiful applications in organic synthesis, however, such are often limited to polymerization or 1,2-difunctionalization. Herein, we disclose unprecedented radical relay 1,4-oxyimination two electronically differentiated with a class bifunctional oxime carbonate reagents via energy transfer strategy. The protocol is highly chemo- regioselective, three different chemical...

Intermolecular carboamination of olefins offers a powerful platform for the rapid construction structurally complex amines from abundant feedstocks. However, these reactions often require transition-metal catalysis, and are mainly limited to 1,2-carboamination. Herein, we report novel radical relay 1,4-carboimination across two distinct with alkyl carboxylic acid-derived bifunctional oxime esters

With over 10,000 new reaction protocols arising every year, only a handful of these procedures transition from academia to application. A major reason for this gap stems the lack comprehensive knowledge about reaction's scope, i.e., which substrates protocol can or cannot be applied. Even though chemists invest substantial effort assess scope protocols, resulting tables involve significant biases, reducing their expressiveness. Herein we report standardized substrate selection strategy...

Transition metal-catalyzed addition of diaryl alkynes with arylating reagents for the synthesis tetraarylethylenes generally encounters rigorous reaction conditions and relies on use prefunctionalized substrates such as organic halides or surrogates organometallic reagents. In this work, we establish a highly trans-selective 1,2-diheteroarylation azoles via rhodium/copper cocatalyzed C–H addition/oxidative coupling process. Moreover, diheteroarylation developed herein could open door...

A great challenge in transition metal-catalyzed oxidative Ar–H/Ar–H cross-coupling chemistry is to develop privileged catalytic platforms for overcoming the restriction specific substrates. Reported herein a Cp*Ir(III) platform broad C–H ortho-heteroarylation of arenes with up 16 types directing groups. The power further demonstrated by (Z)-selective heteroarylation enamides, which clearly different from methods where chain begins metalation heteroarene leading (E)-selective product. Unlike...

Abstract The hydroformylation of alkynes is a fundamental and important reaction in both academic research industry. Conventional methods focus on the conversion alkynes, CO, H 2 into α,β‐unsaturated aldehydes, but they often suffer from problems associated with operation, regioselectivity, chemoselectivity. Herein, we disclose an operationally simple, mild, syngas‐free rhodium‐catalyzed for via formyl hydride transfer alkyl aldehyde. This synthetic method uses inexpensive easy‐to‐handle n...

Abstract The C−C bond formation reaction represents a fundamental and important transformation in synthetic chemistry, exploring new types of reactions is recognized as appealing, yet challenging. Herein, we disclose the first example rhodium‐catalyzed dealkenylative arylation alkenes with arylboronic compounds, thereby providing an unconventional access to bi(hetero)aryls excellent chemoselectivity. In this method, C(aryl)−C(alkenyl) C(alkenyl)−C(alkenyl) bonds various 1,3‐dienes can be...

β-Azolyl propanoic acid derivatives are frequently found in biologically active molecules and pharmaceuticals. Here, we report the oxidative heteroarylation of unactivated C(sp3)-H bonds with azole C(sp2)-H via copper or nickel catalysis aid removable bidentate auxiliary, which provides a rapid pathway to β-azolyl derivatives. A variety azoles such as oxazole, benzoxazole, thiazole, benzothiazoles, benzimidazole, purine, even [1,2,4]triazolo[1,5-a]pyrimidine could be engaged this protocol.

The development of the oxidative cross-coupling unreactive C(sp3)-H bonds with (hetero)arene C(sp2)-H is considerably appealing, yet conceptually and practically challenging. Here, we disclose rhodium-catalyzed heteroarylation unactivated heteroarene bonds. This method provides a step-economic route to β-heteroarylated 2-ethylpyridine derivatives, which exhibits relatively broad substrate scope, high tolerance level sensitive functional groups, selectivity. protocol can also be extended...

Abstract The functionalization of thiophenes is a fundamental and important reaction. Herein, we disclose iridium‐catalyzed one‐pot annulation reactions (benzo)thiophenes with (hetero)aromatic or α,β‐unsaturated carboxylic acids, which afford thiophene‐fused coumarin‐type frameworks. Dearomatization 2‐substituted acids deliver various thiophene‐containing spirocyclic products. occurrence two interconnected provides direct evidence for Heck‐type pathway. mechanistic scenario described herein...

A rhodium(<sc>iii</sc>)-catalyzed oxidative <italic>ortho</italic>-heteroarylation of <italic>N</italic>-nitrosoaniline with heteroarene has been developed for the synthesis (2-aminophenyl)heteroaryls under mild conditions.

Organic BF2 complexes exhibit characteristics such as large Stokes shift, high quantum yield, strong emission intensity, and robust chemical stability, thereby being extensively used in various applications. Herein, we disclose a novel copper-catalyzed cascade C-H activation/acyloxylation difluoroboronation of 2-phenylpyridine derivatives, thus providing straightforward rapid gateway to series N,O-bidentate organic with excellent photophysical properties. Mechanism studies demonstrate that...

The development of organic materials with high solid-state luminescence efficiency is highly desirable because their fundamental importance and applicability in optoelectronics. Herein, a rapid construction novel BF2 complexes N,O-bidentate ligands by using Cu(BF4 )2 •6H2 O as catalyst source disclosed, which avoids the need for pre-composing features broad substrate scope tolerance level sensitive functional groups. Moreover, molecular oxygen employed terminal oxidant this transformation. A...

Durch Koordinationsaktivierung gelingt die oxidative Funktionalisierung der α-C(sp3)-H-Bindungen von α-tertiären α-Aminosäureestern unter Bildung α-quartären α-Aminosäuren. Die Reaktion verfügt über eine große Substratbreite hinsichtlich sowohl α-Aminosäuren als auch Nukleophile (Nu) und ist gut verträglich mit funktionellen Gruppen (siehe Schema, DTBP=Di-tert-butylperoxid, DCE=1,2-Dichlorethan). As a service to our authors and readers, this journal provides supporting information supplied...

Abstract The first example of cobalt‐catalyzed oxidative C−H/C−H cross‐coupling between two heteroarenes is reported, which exhibits a broad substrate scope and high tolerance level for sensitive functional groups. When the amount Co(OAc) 2 ⋅4 H O reduced from 6.0 to 0.5 mol %, an excellent yield still obtained at elevated temperature with prolonged reaction time. method can be extended arene heteroarene. It worth noting that Ag CO 3 oxidant renewable. Preliminary mechanistic studies by...

Described herein is an iridium(<sc>iii</sc>)-catalyzed oxidative Ar–H/Ar–H cross-coupling of primary benzamides with thiophenes for the synthesis (2-thienyl)benzamides.

A mild Rh(<sc>iii</sc>)-catalyzed annulation of <italic>N</italic>-methoxybenzamides with ynesulfonamides has been developed for the synthesis 4-aminoisoquinolone derivatives under external-oxidant-free conditions.

Abstract The hydroformylation of alkynes is a fundamental and important reaction in both academic research industry. Conventional methods focus on the conversion alkynes, CO, H 2 into α,β‐unsaturated aldehydes, but they often suffer from problems associated with operation, regioselectivity, chemoselectivity. Herein, we disclose an operationally simple, mild, syngas‐free rhodium‐catalyzed for via formyl hydride transfer alkyl aldehyde. This synthetic method uses inexpensive easy‐to‐handle n...

Abstract Organische BF 2 ‐Komplexe weisen erstrebenswerte Eigenschaften wie eine große Stokes‐Verschiebung, hohe Quantenausbeute, starke Emissionsintensität und chemische Robustheit auf werden daher in vielen verschiedenen Anwendungen eingesetzt. Hier stellen wir neuartige kupferkatalysierte Kaskaden‐C‐H‐Aktivierung/Acyloxylierung Difluorborierung von 2‐Phenylpyridinderivaten vor, die einen einfachen schnellen Zugang zu einer Reihe N,O‐bidentaten organischen ‐Komplexen mit ausgezeichneten...